3-alkyl-4-hydroxy-s-(dialkylaminoalkyl)-benzyl n, n-dialkyldithiocarbamates and method of prepartion



United States Patent 3 ALKYL 4 S {DIALKYLAMENQ- ALKYL) EENZiL Nn-l DIALKYLDZTHEQCAR- BAMATES AND METHSD Gi PREPARATIQ N Francis X. GShea, Woleott, Conn, assignor to Uniroyal,

lncx, a corp-oration of New Jersey No Erarving. Filed June 9, 1965, Ser. No. 452,745 6 Claims. (Cl. zen-ass ABSTRACT @F 1%., DISQLQSURE Compositions of matter and their method of preparation. The compositions having the following formula:

wherein R is an alkyl, a cycloallryl, or an arallryl radical, R and R are hydrogen or methyl, and R and R are allcyl radicals, are prepared by reacting a phenolic compound with formaldehyde, a secondary a. inc and carbon disulfide. These compounds are useful 'is fungicides and bactericides. The method involves reacting a phenolic compound With formaldehy e, a secondary amine carbon disulfide.

This invention relates to new chemicals. The chemicals of the present invention may be represeated by the general formula:

R CHzNRiR;

wherein R, R and R are as above described, with tWo molar equivalents of formaldehyde, two molar equivalents of a secondary amine of the formula R R Nl-l in which R and R are as above described and one molar equivalent of carbon disulfide in an alcohol solvent. The overall equation for the reaction is:

In carryin out the preparation, the phenolic compound and secondary amine and formaldehyde may be mixed in an alcohol solvent and reacted for a short time at 0 C., the time and temperature not being critical, and the carbon disulfine is then added to the reaction mixture. The reaction mixture is heated to completion of the reaction, usually at the reflux temperature of the alcohol solvent for l to 12 hours, the time and temperature not being critical. If desired, the carbon disulfide may be added initially to the reaction mixture, and the reactions will take place as above. The reactions are as follows:

The second reaction is unique since it is unanticipated that When two such reactive positions, ortho and para to the phenolic hydroxide group, are present, the one para to the phenolic hydroxide reacts preferentially with the carbon disulfide to leave the secondary aminoinethyl group in the ortho position essentially unreactcd.

'l'he hydrocarbon substituted phenols which may be phenol, 6- alpha-methylpentyl -m-cresol, 2- alpha-methylpentyl) 3,5 dimethylphenol, 6-t-amyl-n1-cresol, 2-tamyl 3,5 dimethylphenol, 6(alpha methylheptyD-mcresol, Z-(alpha-methylheptyl) 3,5 dimethylphenol, 6- (alpha-methylnonyl) m cresol, 2-(alpha-methylnonyl)- 3,5-dimethylphenol, 6-( alpha methylundecyl)-m-cresol, Z-(alpha methylundecyl) -3,5-dirnethyl phenol, 6-t-cctylm-cresol, 2-t-octyl-3,S-dimethylphenol, 6-cyclohexyl-mcresol, 2-cyclohexyl-3,S-dimethylphenol, 6-cyclooctyl-mcresol, 2-cyclooctyl 3,5 dimethylphenol, 6-benzyl-mcresol, 2-benzyl-3,S-dimethylphenol, 6-(alpha-methylbenzyl)-m-cresol, Z-(alpha-methylbenzyl) 3,5 xylenol, 6- (alpha,alpha-dimethylbenzyl) m cresol and Z-(alpha, alpha-dimethylbenzyl)-3,5-xylenol. The preferred phenols are o-alkylphenols in which the alkyl group contains from one to four carbon atoms such as o-cresol and o-t-butylphenol. The secondary amines which may be used include dimethylamine, methylethylarnine, diethylamine, dibutylamine, diamylamine. The preferred amine is dimethylamine.

The following chemicals are illustrative of the compounds of the present invention using the above referred hydrocarbon substituted phenols and secondary amines in their preparation:

3 -methyl-4-hydroxy-5- (dirnethyl aminomethyl) -benzyl N,N-dimethyldithiocarb amate 3-t-butyl-4-hydroxy-5- (dimethylaminomethyl) -benzyl N,N-dimethyldithiocarbarnate 3-cyclohexyl-4-hydroxy-5- (dimethylaminomethyl) -benzyl N,N-dimethyldithiocarb amate 3-cyclooctyl-4-hydroxy-5- (dimethylaminomethyl) -benzyl N,N-dimethyldithiocarbamate 3-isopropyl-4-hydroxy-5- (dimethylaminomethyl) -benzyl N,N-dimethyldithiocarbamate 3-sec-butyl-4-hydroxy-5- (dimethylaminomethyl -benzyl N,N-dimethyldithiocarb amate 3- (alpha-methylnonyl -4-hydroxy-5- dimethylaminomethyl) benzyl N,N-dimethyldithiocarbamate 2,5 -dimethyl-3- dimethylaminornethyl) -4-hydroxybenzyl N,N-dimethyldithiocarbamate 2,3-dimethyl-4-hydroxy-5- (dimethylaminomethyl -b enzyl N,N-dimethyldithiocarb amate 3-methyl-4-hydroxy-5- (dibutylaminomethyl) benzyl N,N-dibutyldithiocarb amate 3-rnethyl-4-hydroxy-5- (ethylisopropylaminomethyl) benzyl N-ethyl-N-isopropyldithiocarbamate 3-methyl-4-hydroxy-5- [di(beta-hydroxyethyl aminomethyl] N,N-di (beta-hydroxyethyl) dithiocarbamate 2,6-dimethyl-3- alpha,alpha-dimethylbenzyl -4-hydroxy- 5 dimethylaminomethyl benzyl N,N-dimethyldithiocarbamate 2,6-dimethyl-3- alpha-methylundecyl -4-hydroxy-5- (dimethylaminomethyDbenzyl N,N-dimethyldithiocarb amate Example 1 The preparation of 3-methyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate.

To a solution of 54 g. (0.5 mole) of o-cresol and 190 g. (1.05 mole) of dimethylamine in 250 ml. of ethanol was added 84 g. (1.05 mole) 37% aqueous formaldehyde dropwise with cooling to keep the temperature below C. To the solution was then added 38 g. (0.5 mole) of carbon disulfide and the solution was heated under reflux for three hours. The solution was then cooled and poured into water. The product which separated was extracted with ether.

The ether solution was shaken with a solution of 50 ml. of concentrated HCl in 200 ml. of Water. The other layer rom this extraction yielded a solid precipitate which was filtered off, washed with hexane and dried, wt.=15 g. This 4 Example 2 The preparation of 3-t-butyl-4-hydroxy- 5 (dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate.

Using the method described in Example 1, o-tbuty1- phenol was converted to 3-t-butyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N dimethyldithiocarbamate in 58% yield, M.P. 113-11? 0.

Analysfs.-Calcd for C H N OS C, 60.0%; H, 8.24%; N, 8.24%; S, 18.80%. Found: C, 60.29%; H, 8.16%; N, 8.50% S, 18.66%.

Example 3 The preparation of 3-isopropyl-4-hydroxy-5-(dimethylaminornethyl)benzyl N,N-dimethyldithiocarbamate.

Using the method described in Example 1, o-isopropylphenol was converted to 3-isopr0pyl-4-hydroxy-5-(dimethylarninomethyl)benzyl N,N-dimethyldithiocarbamate in 57% yield, M.P. 79-80 C. after recrystallization from ethanol.

Analysis.Calcd for C H N OS N, 8.59%; S, 19.62%, Found: N, 8.5%; S, 19.62%.

Example 4 The preparation of 3-sec-butyl-4-hydroxy-5-(dimethylaminomethyDbenzyl N,N-dimethyldithiocarbamate.

Using the method described in Example 1, o-sec-butylphenol was converted to 3-sec-butyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N dimethyldithiocarbamate in 50% yield, M.P. --91 C. after recrystallization from ethanol.

AnalysiS.Calcd for C17H28N2OS2: N, S, 18.80%, Found: N, 8.20%; S, 19.11%.

Example 5 The preparation of 3-(alpha-methylnonyl)-4-hydroxy- 5 dimethylaminomethyl) benzyl N,N-dimethyldithiocarbamate. A

Using the method described in Example 1, o-(alphamethylnonyl)phenol was converted to 3-(alpha-methyl nonyl)-4 hydroxy 5 (dimethylaminomethyl) phenol in 72% yield. This product was a viscous oil.

Example 6 The preparation of 2,5-dimethyl 3 (dimethylaminomethyl)-4-hydroxybenzyl N,N-dimethyldithiocarbamate.

To a solution of 122 g. (1 mole) of 2,5-dimethylphenol and 360 g. (2 moles) of 25% dimethylamine in 200 ml. of ethanol was added 162 g. (2 moles) of 37% aqueous formaldehyde dropwise with cooling to keep the temperature below 30 C. Carbon disulfide (77 g., 1 mole) was then added and the reaction mixture was heated under reflux for four hours. It was then poured into water and the precipitate which formed was filtered off and washed with ethanol. The yield of 2,5-dimethyl-3-(dirnethylaminomethyl) 4 hydroxybenzyl N,N dimethyldithiocar- Example 7 The preparation of 2,3-dimethyl-4-hydroxy-5 -(dimetl1ylaminomethyl)-benzyl N,N-dimethyldithiocarbamate.

Using the method described in Example 1, 2,3-dimethylphenol was converted to 2,3-dimethyl-4-hydroxy-5-(dimethylaminomethyl) benzyl N,N-dimethyldithiocarbamate in 91% yield, M.P. 909l C. after recrystallization from methanol.

Example 8 The prepartion of 3-cyclohexyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate.

To a solution of 88 g. (0.5 mole) of o-cyclohexylphenol and 190 g. (1.05 mole) of 25% aq. dimethylamine in 500 ml. of ethanol was added 84 g. (1.05 mole) of 37% aq. formaldehyde with cooling to keep the temperature below 30 C. The solution was stirred at room temperature for one hour and then was heated at reflux for two hours. The solution was cooled, carbon disulfide (53 g., 0.7 mole) was added, and the solution was heated at reflux for two hours.

The reaction mixture was diluted with Water and the product was extracted with benzene. The benzene layer was filtered to remove some insoluble material. It was then shaken with dilute hydrochloric acid and the acidic extract was separated and neutralized with aqueous sodium carbonate. The product which separated was extracted with benzene, washed with water, dried over anhyd. sodium sulfate and evaporated down to yield 127 g. (74%) of 3-cyclohexyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate, M.P. 98- 100 C. after recrystallization from hexane.

Example 9 The preparation of 3-cyclooctyl-4-hydroxy-5-(dimethylaminomethyl) benzyl N,N-dimethyldithiocarbamate.

To a solution of 62 g. (0.19 mole) of o-cyclooctylphenol and 68.4 g. (0.38 mole) of 25% aq. dimethylamine in 200 ml. of ethanol was added 30.8 g. (0.38 mole) of 37% aqueous formaldehyde with cooling to keep the temperature below 30 C. Carbon disulfide (14.4 g., 0.19 mole) was added and the solution was heated at reflux for five hours.

The reaction mixture was diluted with water and the product was extracted with ether. The ether layer was then shaken with dilute hydrochloric acid and the acidic extract was separated and neutralized with aqueous sodium carbonate. The product which separated was extracted with ether, washed with water, dried over anhyd. sodium sulfate and evaporated down to yield 3-cycloocty1- 4 hydroxy 5 (dimethylaminornethyl)benzyl N,N dimethyldithiocarbamate as a liquid residue.

In view of the many changes and modifications that may be made without departing from the principles underlying the invention, reference should be made to the appended claims for an understanding of the scope of the protection afforded the invention.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A compound having the general formula R CH2NR3R4 wherein R is selected from the group consisting of alkyl radicals of up to 12 carbon atoms and cycloalkyl radicals of 5 to 8 carbon atoms and aralkyl radicals of 7 to 9 carbon atoms, R and R are selected from the group consisting of hydrogen and methyl, R and R are selected from the group consisting of alkyl radicals having up to 5 carbon atoms each.

2. 3 methyl 4 hydroxy 5 (dimethylam-inomethyl) benzyl N,N-dimethyldithiocarbamate.

3. 3 t butyl 4 hydroxy 5 (dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate.

4. 3 cyclooctyl 4 hydroxy 5 (dimethy1amino methyl)benzyl N,N-dimethyldithiocarbamate.

5. 2,3 dimethyl 4 hydroxy 5 (dimethylaminomethyl)benzyl, N,N-dimethyldithiocarbamate.

6. The method of preparing a compound having the general formula R- CII2NRaR4 Ri R2 wherein R is selected from the group consisting of alkyl radicals of up to 12 carbon atoms and cycloalkyl radicals of 5 to 8 carbon atoms and aralkyl radicals of 7 to 9 carbon atoms, R and R are selected from the group consisting of hydrogen and methyl, R and R are selected from the group consisting of alkyl radicals having up to 5 carbon atoms each, which comprises reacting one molar equivalent of a phenolic compound of the formula wherein R, R and R are as above described, with two molar equivalents of formaldehyde, two molar equivalents of a secondary amine of the formula R R NH in which R and R are as above described, and one molar equivalent of carbon disulfide.

References Cited UNITED STATES PATENTS 2,757,174 7/1956 Hardman 260-455 X CHARLES B. PARKER, Primary Examiner. B. BILLIAN, D. R. PHILLIPS, Assistant Examiners. 

